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| United States Patent |
5,274,047
|
|
Koenhen
, et al.
|
December 28, 1993
|
Semipermeable composite membrane, a process for the manufacture thereof,
as well as application of such membranes for the separations of
components in an organic liquid phase or in the vapor phase
Abstract
Semipermeable composite membrane, with a porous carrier substrate, whereby
said carrier substrate is provided with a polymer network obtained by
polycondensation, especially interfacial polymerization, which is built up
of at least one reactive polyfunctional monomer or oligomer or prepolymer
or polymer, and at least one acid halide containing polymer.
The specialty of this semi-permeable composite membrane consists therein
that the acid halide containing polymere itself is built up of one or more
vinyl containing monomers.
The acid halide containing polymer is generally a copolymer of
acryloylchloride H.sub.2 C.dbd.CHCOCl or methacryloyl chloride H.sub.2
C.dbd.C(CH13)COCl with one or more vinyl containing monomers.
Usually the vinyl containing monomer is an acrylate or an acrylamide or a
mixture thereof.
The invention further relates to a process for the manufacture of such
membranes, as well as a method for the separation of components in an
organic liquid phase or in the vapor phase using a semipermeable composite
membrane according to the invention.
| Inventors:
|
Koenhen; Dirk M. (Dedemsvaart, NL);
Tinnemans; Aloysius H. A. (Zeist, NL)
|
| Assignee:
|
X-Flow B.V. (Almelo, NL)
|
| Appl. No.:
|
839186 |
| Filed:
|
February 21, 1992 |
Foreign Application Priority Data
| Current U.S. Class: |
525/329.7; 210/500.27; 210/500.35; 210/500.38; 210/500.42; 210/654; 427/244; 427/245; 521/64; 525/293; 525/296; 525/329.4; 525/330.7; 528/345; 528/350 |
| Intern'l Class: |
B01D 069/12; C08F 020/00 |
| Field of Search: |
525/329.7,293,296,329.4,330.7
521/64
528/345,350
210/654,500.27,500.35,500.38,500.42
427/244,245
|
References Cited
U.S. Patent Documents
| 4721568 | Jan., 1988 | Buys et al. | 210/500.
|
| 5039421 | Aug., 1991 | Linder et al. | 210/654.
|
| Foreign Patent Documents |
| 0254556 | Jan., 1988 | EP.
| |
Other References
Abstract of Swiss Patent No. 470,430 (L'Oreal); English Language Abstract
of Patents Abstracts of Japan, vol. 13, No. 190.
An English Abstract of Patents Abstracts of Japan, vol. 3, No. 95; Copy of
Swiss Patent No. 470,430.
|
Primary Examiner: Kight, III; John
Assistant Examiner: Cooney, Jr.; John M.
Attorney, Agent or Firm: Brooks Haidt Haffner & Delahunty
Claims
We claim:
1. A semipermeable composite membrane for the separation of components in
an organic liquid phase, said membrane having a porous carrier substrate,
wherein said carrier substrate has a polymer network obtained by
polycondensation of (A) at least one reactive polyfunctional monomer,
oligomer, prepolymer or polymer having --NHR.sub.4, --OH or --SH as
functional groups, wherein R.sub.4 is H or an C.sub.1 -C.sub.20 alkyl and
(B) at least one or more acid halide containing polymers having --COX,
--SO.sub.2 X, --POXR.sub.5 or --NR.sub.6 COX functional groups,
wherein X represents Cl, Br or I, and
wherein R.sub.5 and R.sub.6 each represent an alkoxy or alkyl group having
1-16 carbon atoms,
characterized in that said acid halide containing polymer is a copolymer
with one or more vinyl containing monomers, and said polymer network is
void of functional groups of formula I:
##STR5##
2. A semipermeable composite member according to claim 1, characterized in
that said polycondensation is interfacial polymerization.
3. A semipermeable composite member according to claim 1, characterized in
that R.sub.5 and R.sub.6 each represent an alkoxy or alkyl group having
1-5 carbon atoms.
4. A semipermeable composite membrane according to claim 1, characterized
in that the mole fraction of said acid halide containing monomer in the
polymer is 1-20%.
5. A semipermeable composite membrane according to claim 4, characterized
in that the mole fraction of said acid halide containing monomer in the
polymer is 5-11%.
6. A semipermeable composite membrane according to claim 1, characterized
in that the polymer network further comprises a reactive polyfunctional
monomer or oligomer having --COX, --SO.sub.2 X, --POXR.sub.5, --NR.sub.6
COX or --NCO as reactive groups,
wherein X represents Cl, Br or I, and
wherein R.sub.5 and R.sub.6 each represent an alkoxy or alkyl group having
1-16 carbon atoms.
7. A semipermeable composite membrane according to claim 6, characterized
in that R.sub.5 and R.sub.6 each represent an alkoxy or alkyl group having
1-5 carbon atoms.
8. A semipermeable composite membrane according to claim 6, characterized
in that the reactive polyfunctional monomer is isophthaloyl chloride.
9. A semipermeable composite membrane according to claim 1, characterized
in that the acid halide containing polymer is a copolymer of acryloyl
chloride H.sub.2 C.dbd.CHCOCl or methacryloyl chloride H.sub.2
C.dbd.C(CH.sub.3)COCl having one or more vinyl monomers.
10. A semipermeable composite membrane according to claim 1, characterized
in that the vinyl containing monomer is an acrylate with the formula:
##STR6##
wherein R.sub.1 and R.sub.2 represent H, an C.sub.1 -C.sub.20 alkyl, or an
aryl.
11. A semipermeable composite membrane according to claim 10, characterized
in that said aryl is phenyl.
12. A semipermeable composite membrane according to claim 10, characterized
in that said aryl is naphthyl.
13. A semipermeable composite membrane according to claim 10, characterized
in that R.sub.2 represents OH, halogen, siloxane or alkoxy.
14. Semipermeable composite membrane according to claim 10, characterized
in that the vinyl containing monomer is isobutyl methacrylate.
15. Semipermeable composite membrane according to claim 10, characterized
in that the vinyl containing monomer is a mixture of isobutyl methacrylate
and trifluorethyl acrylate.
16. Semipermeable composite membrane according to claim 10, characterized
in that the vinyl containing monomer is a mixture of isobutyl methacrylate
and ethyl acrylate.
17. Semipermeable composite membrane according to claim 10, characterized
in that the vinyl containing monomer is a mixture of isobutyl methacrylate
and N-vinyl pyrrolidone.
18. Semipermeable composite membrane according to claim 10, characterized
in that the vinyl containing monomer is a mixture of isobutyl methacrylate
and N-vinyl-N-methyl acetamide.
19. Semipermeable composite membrane according to claim 10, characterized
in that the vinyl containing monomer is a mixture of isobutyl methacrylate
and acrylate acid.
20. Semipermeable composite membrane according to claim 10, characterized
in that the vinyl containing monomer is methyl methacrylate.
21. Semipermeable composite membrane according to claim 10, characterized
in that the vinyl containing monomer is ethyl acrylate.
22. Semipermeable composite membrane according to claim 10, characterized
in that the vinyl containing monomer is 2-ethylhexyl acrylate.
23. A semipermeable composite membrane according to claim 13, characterized
in that said alkoxy is an C.sub.1 -C.sub.10 alkoxy.
24. A semipermeable composite membrane according to claim 1, characterized
in that the vinyl containing monomer is an acryl amide with the formula:
##STR7##
wherein one or more R.sub.1, R.sub.2 and R.sub.3 represent H or an C.sub.1
-C.sub.20 alkyl.
25. A semipermeable composite membrane according to claim 24, characterized
in that one or more R.sub.1, R.sub.2 and R.sub.3 represent OH, halogen or
aryl.
26. A semipermeable composite membrane according to claim 25, characterized
in that one or more of said R.sub.1 or R.sub.2 is aryl.
27. A semipermeable composite membrane according to claim 26, characterized
in that said aryl is phenyl.
28. A process for the manufacture of a semipermeable composite membrane for
the separation of components in an organic liquid phase by coating a
porous substrate with a polymer network which is void of functional groups
of formula I:
##STR8##
obtained by polycondensation, characterized in that: the porous substrate
is treated in a first treatment with a solution of at least one reactive
polyfunctional monomer, oligomer, prepolymer or polymer having
--NHR.sub.4, --OH or --SH as functional groups, wherein R.sub.4 is a H or
a C.sub.1 -C.sub.20 alkyl;
after which the substrate is further treated in a second treatment with a
solution of at least one acid halide containing polymer with --COX,
--SO.sub.2 X, --POXR.sub.5, --NR.sub.6 COX or --NCO as reactive groups,
wherein X represents Cl, Br or I, and
wherein R.sub.5 and R.sub.6 each represent an alkoxyl or alkyl group having
1-16 carbon atoms and wherein said acid halide containing polymer is a
copolymer with one or more vinyl containing monomers in a suitable organic
solvent; and
after which the substrate is dried.
29. A process for the manufacture of a semipermeable composite membrane
according to claim 28, characterized in that said polycondensation is
interfacial polymerization.
30. A process for the manufacture of a semipermeable composite membrane
according to claim 28, characterized in that the solution in said first
treatment includes a surface active compound in water.
31. A process for the manufacture of a semipermeable composite membrane
according to claim 28, characterized in that R.sub.5 and R.sub.6 each
represent an alkoxyl or alkyl group with 1-5 carbon atoms.
32. A process for the manufacture of a semipermeable composite membrane
according to claim 28, characterized in that said process further includes
a subsequent heat treatment.
33. A process for the separation of components in an organic liquid or
vapor phase using a semipermeable composite membrane with a porous carrier
substrate on which an applied polymer network is obtained by
polycondensation, characterized in that the organic liquid or vapor phase
is contacted with a semipermeable composite membrane according to claim 1.
34. Method for the separation of components according to claim 33,
characterized in that said polycondensation is interfacial polymerization.
Description
The invention relates to a semipermeable composite membrane, with a porous
carrier substrate, whereby said carrier substrate is provided with a
polymer network, obtained by polycondensation, especially interfacial
polymerization, which is built up of at least one reactive polyfunctional
monomer or oligomer or prepolymer or polymer with as functional groups
--NHR.sub.4 (R.sub.4 .dbd.H or alkyl with C.sub.1 --C.sub.20), --OH or
--SH and at least one acid halide containing polymer with as functional
groups --COX, --SO.sub.2 X, --POXR.sub.5 or --NR.sub.6 COX, wherein X
represents Cl, Br or I, while R.sub.5 and R.sub.6 each represent an alkoxy
group or an alkyl group with 1-16 carbon atoms, preferably 1-5 carbon
atoms, as well as to a process for the manufacture of such membranes and
finally to a method for the separation of components in an organic liquid
phase or in the vapour phase.
Such composite membranes suitable for reverse osmosis and obtained by
interfacial polymerization, are already known. The article Evolution of
Composite Reverse Osmosis Membranes of J. E. Cadotte, American Chemical
Society, 1985, discloses for instance the development of a series of
composite membranes, which have resulted in the commercial FT-30 membrane
manufactured by interfacial polymerization of aromatic diamines in the
aqueous phase with triacyl chlorides in the organic phase (page 279 and
following), with as principal application desalination of aqueous
solutions. Further, still reference may be made to the U.S. Pat. No.
4,721,568. For another good review it is referred to the U.S. Pat. No.
4,360,434 (Kawaguchi et al.). This patent describes amphoteric
ion-permeable composite membranes and shows at page 32 which types of
monomeric diacid chlorides may be applied therefore.
With the above described FT-30 membranes reverse osmosis tests have been
carried out in non-aqueous systems, whereby the separation results
obtained in a methanolic environment are listed in Table A.
From reverse osmosis test of the above FT-30 membrane in a non-aqueous
system it follows that:
a. no n-hexane flux (1%, by weight, of n-docosane in n-hexane at room
temperature and at 40 bar) is observable
b. there is no toluene flux (the same in toluene)
c. in a 1%, by weight, solution of PEG 300 in methanol a good retention for
PEG 300 (93%) is found but a moderate methanol flux of 30
kg/(m.sup.2.hour).
From these data the following conclusions may be drawn.
Applicant prepared composite membranes from aromatic diacid
chlorides+aliphatic polyfunctional amines.
Such membranes have been submitted to reverse osmosis tests with the
following result:
a. no n-hexane and no n-toluene flux
b. in methanol moderate to bad methanol fluxes 4-13 kg/(m.sup.2.hour) and
moderate retentions for PEG 300 (53-68%).
Subsequently membranes have been prepared from aliphatic diacid
chlorides+aliphatic polyfunctional amines, with the following result:
a. no n-hexane and toluene flux; not even when large hydrophobic moieties
are introduced, while using ClOC(CH.sub.2).sub.8 COCl
b. in some cases in methanol results may be obtained, which are comparable
as in case of a FT-30 membrane (good retention/moderate flux); in some
cases better flux values, but somewhat worse retentions (the latter is not
desirable!).
From the above may be concluded that this type of membrane built up of
aromatic and/or aliphatic diacid chlorides+polyfunctional (aromatic or)
aliphatic amines is unsuitable for application in n-hexane (C.sub.5
-C.sub.8 aliphatic) or toluene (aromatic) systems. On the other hand, in
methanol good retentions may be obtained for PEG 300, but at low fluxes.
The known membranes with monomeric or oligomeric polyacid halides have
further in general the disadvantage that they do not show a swelling, have
a small mesh size, are rigid, and have a high polarity. Further, there are
known composite membranes, which are built up of polymeric diacid
chlorides+polyfunctional amine. In this respect mention is made of EP 0
254 556 (Bend Research Inc.). The polymeric diacid chloride comprises
terminal acid chlorides with a polymeric middle part
##STR1##
It is known that this middle part has a high affinity to n-hexane and
toluene, and is therefore suitable for application in R.O. (reverse
osmosis) composite membranes in this type of solvents. However, the used
prepolymers based on siloxanes comprise as terminal groups --NCO.
The membranes described according to this European patent application are
suitable for the separation of gases. Not a word is mentioned in the
European patent application EP 0 254 556 about the application of such
membranes for the separation of components in an organic liquid phase or
in the vapor phase.
It is observed that the middle part
##STR2##
is responsible for the affinity of the top layer for RO separations in an
organic environment. Beside the terminal acid chloride groups this is an
essential limitation to tune the affinity of the top layer (and thus the
flux and retention behavior) to the solvent stream wherein the separation
takes place.
Now the invention intends to provide semipermeable composite membranes,
which eliminate the disadvantages inherent to the known membranes and
which are suitable for the separation of components in an organic liquid
medium at a good flux and a good retention.
To this end the invention provides a semipermeable composite membrane, with
a porous carrier substrate, whereby said carrier substrate is provided
with a polymer network obtained by polymerization, especially by
interfacial polymerization, which network is built up of at least one
reactive polyfunctional monomer or oligomer or prepolymer or polymer with
as functional groups --NHR.sub.4 (R.sub.4 .dbd.H or alkyl with C.sub.1
-C.sub.20), --OH or --SH and at least one acid halide containing polymer
with as functional groups --COX, --SO.sub.2 X, --POXR.sub.5 or --NR.sub.6
COX, wherein X represents Cl, Br or I, while R.sub.5 and R.sub.6 each
represent an alkoxy group or an alkyl group with 1-16 carbon atoms,
preferably 1-5 carbon atoms, characterized in that the acid halide
containing polymer itself is built up from one or more vinyl containing
monomers.
Surprisingly it appeared that the semipermeable membranes according to the
invention, which are novel, are especially suitable for the separation of
components in an organic liquid phase or in the vapor phase, for instance
polyethylene glycol in methanol, n-docosane in n-hexane, etc. Moreover the
membranes according to the invention do not appear to show practically any
swelling, they have a substantial mesh size, they are flexible, they have
a larger affinity for organic liquids owing to a lower polarity.
In general the mole fraction of the acid halide containing monomer in the
polymer amounts to 1-20 and preferably 5-11% in case of the semipermeable
composite membranes according to the invention.
It has appeared that it may be favorable when the polymer network moreover
comprises a reactive polyfunctional monomer or oligomer with as reactive
groups --COX, --SO.sub.2 X, --POXR.sub.5, --NR.sub.6 COX or NCO, wherein X
represents Cl, Br or I, while R.sub.5 and R.sub.6 each represent an alkoxy
group or an alkyl group with 1-6 carbon atoms, preferably 1-5 carbon
atoms.
An example of an often used reactive polyfunctional monomer is isophthaloyl
chloride.
According to the invention it is preferable when the acid halide containing
polymer is a copolymer of acryloyl chloride H.sub.2 C.dbd.CHCOCl or
methacryloyl chloride H.sub.2 C.dbd.C(CH.sub.3)COCl with one or more vinyl
containing monomers.
Especially favorable are those semipermeable composite membranes according
to the invention, whereby the vinyl containing monomer is an acrylate with
the formula
##STR3##
wherein R.sub.1 and R.sub.2, whether or not equal to each other, represent
H, a C.sub.1 -C.sub.20 alkyl, an aryl like phenyl, naphthyl, etc., while
R.sub.2 is whether or not substituted by an OH, halogen, siloxane, OR,
wherein R is a whether or not substituted C.sub.1 -C.sub.10 alkyl.
Moreover the semipermeable composite membranes according to the invention
appear to satisfy properly when the vinyl containing monomer is an acryl
amide with the formula
##STR4##
wherein R.sub.1, R.sub.2 and R.sub.3, whether or not equal to each other,
represent H, a C.sub.1 -C.sub.20 alkyl, whether or not substituted by OH,
halogen, etc., an aryl like phenyl, naphthyl.
Satisfactory separation results are obtained with membranes, wherein the
vinyl containing monomer is isobutyl methacrylate, a mixture of isobutyl
methacrylate and trifluorethyl acrylate, a mixture of isobutyl
methacrylate and ethyl acrylate, a mixture of isobutyl methacrylate and
N-vinyl-pyrrolidon, a mixture of isobutyl methacrylate and
N-vinyl-N-methylacetamide, a mixture of isobutyl methacrylate and acrylic
acid, methyl methacrylate, ethyl acrylate or 2-ethyl-hexyl acrylate.
Examples of other suitable vinyl containing monomers are N-vinyl
pyrrolidon, vinyl acetate, butadiene, styrene, vinyl ethers like
C.dbd.C--O--R, vinyl chloride, vinylidene chloride, isobutylene,
acrylonitrile, vinyl pyridine.
Further the invention comprises a process for the manufacture of a
semipermeable composite membrane by coating a porous substrate with a
polymer network obtained by polycondensation, especially interfacial
polymerization, characterized in that the porous substrate is treated with
a solution of at least one reactive polyfunctional monomer or oligomer of
prepolymer or polymer with as reactive groups --NHR.sub.4 (R.sub.4 .dbd.H
or alkyl with C.sub.1 -C.sub.20), --OH or --SH and possibly a surface
active compound in water, after which the substrate treated in this manner
is further treated with a solution of at least one acid halide containing
polymer with as reactive groups --COX, --SO.sub.2 X, --POXR.sub.5,
--NR.sub.6 COX or --NCO, wherein X represents Cl, Br or I, while R.sub.5
and R.sub.6 each represent an alkoxy group or alkyl group with 1 to 16
carbon atoms, preferably 1 to 5 carbon atoms, in a suitable organic
solvent, after which the substrate treated in this manner is dried and
subsequently optionally subjected to a heat treatment.
Finally the invention extends to a method for the separation of components
in an organic liquid phase or in a vapor phase using the above described
semipermeable composite membranes according to the invention.
The invention is now further elucidated by the following non-limitative
examples.
EXAMPLE I
A wet flat support membrane of polyimide (0.30.times.0.18 m), prepared from
a 16%, by weight, solution of a polyimide-type (Lenzing, p84) in DMF, was
applied to a cylindrical body manufactured of polyethylene. This support
membrane was dipped for 15 minutes in an aqueous phase with 1.0%, by
weight, H2N--CH2--CH2--CH2--NH--CH2--CH2--NH--CH2--CH2--CH2--NH2 (N4) as
polyfunctional monomer and 0.04%, by weight, of sodium dodecyl sulphate as
surface active compound. Then the membrane was taken out of the aqueous
phase, after which the excess of aqueous solution was removed with a
rubber roller press. After about 1 minute the membrane was transported to
an organic phase, consisting of toluene/chloroform (96/4 g/g) with
dissolved therein 0.05%, by weight, of isotaloyl chloride (IPC) and 0.6%,
by weight, of poly(isobutyl methacrylate-coacryloyl chloride) (molar
proportion 95/5; .eta. intrinsic viscosity 0.53 dl/g in aceton, c=0.5),
obtained after complete conversion during solution polymerization of a
solution of 53.7%, by weight, of the corresponding monomers in chloroform
in the presence of 0.5 mol. % 2,2'-azobis (2-ethyl propionitrile) (AIBN)
as a radical initiator. The membrane was for about 1 minute in the organic
phase. Further the membrane was dried for about 3 minutes at room
temperature, transferred to a flat glass plate and thereafter dried for 15
minutes in an air circulation oven at 90.degree. C.
The reverse osmosis properties of this membrane were evaluated at room
temperature at 40 bar in a solution of 1.0%, by weight, of polyethylene
glycol (PEG 300, Fluka) in methanol with as a result a methanol flux of 89
kg/(m.sup.2.hour) and a retention PEG 300 of 86%.
Comparative example Ia
The procedure of example I was repeated on the understanding that the
organic phase contained, beside IPC, the non-reactive polymer
poly(isobutyl methacrylate). In a reverse osmosis experiment as described
in example I this membrane showed a methanol flux of 35 kg/(m.sup.2.hour)
and a retention PEG 300 of 81%. From the above the favorable effect of the
acid chloride groups built into the polymer on the methanol flux and
retention PEG 300 shows clearly.
Example II
In an analogous manner as described in example I a composite membrane was
prepared. The organic phase, however, comprised toluene-hexane (14/86 g/g)
with dissolved therein a copolymer built up of isobutyl methacrylate
(i-BMA) and acryloyl chloride. As a control, example IIa, a composite
membrane was made with as barrier layer poly(isobutyl methacrylate).
The results of the flux and retention tests of a reverse osmosis experiment
in a 1.0%, by weight, solution of n-docosane in n-hexane, executed at room
temperature and at 40 bar, are mentioned in Table B.
Example III
The procedure of example I was repeated on the understanding that the
organic phase contained, beside 0.05%, by weight, IPC, 0.6%, by weight, of
poly(isobutyl methacrylate-co-acryloyl chloride) (molar ratio 89/11; .eta.
intrinsic 0.56 dl/g in aceton, c=0.5), obtained after complete conversion
during solution polymerization of a 57%, by weight, solution of the
corresponding monomers in chloroform in the presence of 0.5 mol. % AIBN as
a radical initiator.
The results of the flux and retention tests showed a methanol flux of 99
kg/m.sup.2.hour and a retention PEG 300 of 87%.
Example IV
In the manner described in example I a composite membrane was prepared. The
organic phase consisted of freon, toluene, toluene/hexane (10/90 g/g), or
toluene/chloroform
The results of the flux and retention tests of 1.0%, by weight, solutions
of n-docosane in n-hexane and in toluene and of a 1.0%, by weight,
solution of PEG 300 in methanol, evaluated at room temperature and a
pressure of 40 bars, are mentioned in Table C.
Example V
In the manner described in example I a composite membrane was prepared. The
organic phase consisted of freon with dissolved therein 0.61%, by weight,
of poly(isobutyl methacrylate-co-acryloyl chloride) (molar ratio 95/5;
intrinsic 1.96 dl/g in aceton c=0.5), obtained after 65% conversion during
solution polymerization of a 41.7%, by weight, solution of the
corresponding monomers in chloroform in the presence of 0.03 mol. % of
AIBN as a radical initiator. The aqueous phase comprised 1.0%, by weight,
of one of the following polyfunctional amines, to wit
H2N--(CH2--CH2--NH).sub.n --CH2--CH2--NH2 [n=0(2N), n=2(4N), n=4(6N)].
The results of the flux and retention tests, executed in a corresponding
manner as described in example IV, are mentioned in table D.
Example VI
In the manner described in example V a composite membrane was prepared. The
aqueous phase contained 1.0%, by weight, of the polyfunctional amine N4,
as well as 1.0%, by weight, of triethyl amine as an acid binding agent. As
a control a composite membrane was made without the addition of triethyl
amine, comparative example Va. The flux and retention tests of a 1.0%, by
weight, solution of n-docosane in n-hexane are mentioned in Table E.
From example VI and VIa follows that the addition of an acid scavenger to
the aqueous phase has a considerable influence on both the retention
n-docosane and the flux.
Comparison of the results of example IVa and VIa shows the influence of the
molecular weight of the applied copolymer in the organic phase on both the
n-hexane flux and the retention n-docosane.
Example VII
One acts in the manner described in example I in the preparation of a
composite membrane. However, the organic phase consisted of
toluene/n-hexane with dissolved therein a copolymer, built up of isobutyl
methacrylate (i-BMA), 1,1,1-trifluor ethyl acrylate (TFEA) and acryloyl
chloride (AC), obtained after a substantially quantitative conversion
during solution polymerization of a 30.7-31.5%, by weight, solution of the
corresponding monomers in chloroform in the presence of 0.5 mol. % AIBN as
a radical initiator.
The flux and retention tests of a 1.0%, by weight, solution of n-docosane
in n-hexane and in toluene are mentioned in Table F.
Example VIII
One acts in the manner described in example I in the preparation of a
composite membrane. However, the organic phase consisted of
toluene/n-hexane with dissolved therein a copolymer, built up of isobutyl
methacrylate (i-BMA), ethyl acrylate (EA) and acryloyl chloride (AC),
obtained after a substantially, quantative conversion during solution
polymerization of a 36.9-49.6%, by weight, solution of the corresponding
monomers in chloroform in the presence of 0.5 mol. % AIBN as a radical
initiator.
The flux and retention tests, executed in a corresponding manner as in
example VII, are mentioned in Table G.
Example IX
One acts in the manner described in example I in the preparation of a
composite membrane. The organic phase consisted of toluene/n-hexane (42/58
g/g) with dissolved therein poly(isobutyl methacrylate-co-vinyl
pyrrolidon-coacryloyl chloride) (molar ratio 90/5/5, .eta. intrinsic 0.44
dl/g in aceton, c=0.5), obtained after 85% conversion during solution
polymerization of a 36.3%, by weight, solution of the corresponding
monomers in chloroform in the presence of 0.5 mol. % HIBN as the radical
initiator.
The flux and retention tests, executed in a corresponding manner as in
example VII, give as a result in n-hexane a n-hexane flux of 49
kg/(m.sup.2.hour) and a retention n-docosane of 52% and in toluene a
toluene flux of 190 kg/(m.sup.2.hour) and a retention n-docosane of 36%.
Example X
One acts in the manner described in example I in the preparation of a
composite membrane. However, the organic phase consisted of
toluene/n-hexane (77/23 g/g) with dissolved therein 0.64%, by weight, of
poly(isobutyl methacrylate-co-N-vinyl-N-methyl acetamide-co-acryloyl
chloride) (molar ratio 80/15/5, .eta. intrinsic 0.83 dl/g in aceton,
c=0.5), obtained after 74% conversion during solution polymerization of a
71.6%, by weight, solution of the corresponding monomers in chloroform in
the presence of 0.5 mol. % AIBN as the radical initiator.
The reverse osmosis properties of this membrane were evaluated in a
corresponding manner as in example VII, in n-hexane with as a result a
n-hexane flux of 37 kg/(m.sup.2.hour) and a retention n-docosane of 71%
and in toluene a toluene flux of 231 kg/(m.sup.2.hour) and a retention
n-docosane of 63%.
Example XI
One acts in the manner described in example I in the preparation of a
composite membrane. The organic phase consisted of toluene with dissolved
therein a copolymer built up of isobutyl methacrylate (i-BMA), acrylic
acid (AZ) and acryloyl chloride, (AC), obtained after 89% conversion
during solution polymerization of a 39.3%, by weight, solution of the
corresponding monomers in chloroform in the presence of 0.5 mol. % AIBN as
the radical initiator. As a control a composite membrane was made starting
from poly-isobutyl methacrylate-co-acryloyl chloride) (molar ratio 95/5).
The flux and retention tests, executed in a corresponding manner as in
example IV, are mentioned in Table H.
Example XII
One acts in the manner described in example I in the preparation of a
composite membrane. The organic phase consisted of toluene with dissolved
therein 1.57%, by weight, of poly(methyl methacrylate-co-acryloyl
chloride); molar ratio 95/5; .eta. intrinsic (0.84 dl/g in aceton, c=0.5),
obtained by solution polymerization of a 51.5%, by weight, solution of the
corresponding monomers in chloroform in the presence of 0.5 mol. % AIBM as
the radical initiator.
The flux and retention tests were executed in a corresponding manner as in
example IV, with as a result a hexane flux of 0 kg/(m.sup.2.hour), a
toluene flux of 34 kg/(m.sup.2.hour) and a retention n-docosane of 69%,
and a methanol flux of 26 kg/(m.sup.2.hour) and a retention PEG 300 of
68%.
Example XIII
One acts in the manner described in example I in the preparation of a
composite membrane. The organic phase consisted of toluene with dissolved
therein 1.94%, by weight, poly(2-ethylhexyl acrylate-co-acryloyl
chloride); molar ratio 95/5; obtained after 91% conversion during solution
polymerization of a 53.2%, by weight, solution of the corresponding
polymers in chloroform in the presence of 0.5 mol. % AIBM as the radical
initiator.
The flux and retention tests were executed in a corresponding manner as in
example IV, with as a result a hexane flux of 0 kg/(m.sup.2.hour), a
toluene flux of 180 kg/(m.sup.2.hour) and a retention n-docosane of 34%.
TABLE A
__________________________________________________________________________
R.O. test data.sup.3
Acid chloride in Amine in Retention
Methanol flux
organic phase.sup.1
(perc., by weight,)
aqueous phase
(perc., by weight,)
PEG 300 (%)
kg/(m.sup.2 .multidot.
hour)
__________________________________________________________________________
Trimesoyl chloride.sup.2
m-phenylene diamine 93 30
Trimesoyl chloride
0.81 PEI/n4 1/1 53 4
Isophthaloyl chloride
0.81 " 68 12
Isophthaloyl chloride
0.74 " 68 13
Trimesoyl chloride
0.07
ClOC(CH.sub.2).sub.2 COCl
0.81 " 74 77
ClOC(CH.sub.2).sub.2 COCl
0.81 " 51 116
ClOC(CH.sub.2).sub.2 COCl
0.81 PEI/6N 1/1 83 28
ClOC(CH.sub.2).sub.2 COCl
0,81 N4 1 69 60
__________________________________________________________________________
.sup.1 1,1,2trifluor trichlorethane
.sup.2 Commerically obtainable FT30 membrane (Film Tech)
.sup.3 Composite membranes showed no nhexane flux and no toluene flux in
solutions containing 1 perc., by weight, of ndocosane
TABLE B
______________________________________
n-hexane
Copolymer i-BMA/AC flux
molar intr.* perc., by
retention kg/m.sup.2 .multidot.
Example
ratio (dl/g) weight,
n-docosane (%)
hour
______________________________________
IIa 100/-- 0.48 0.54 38 22
IIb 98/2 0.44 0.62 67 21
IIc 95/5 0.53 0.65 73 18
______________________________________
*Evaluated in acetone, c = 0,5
From this example follows clearly the favourable effect of the buildingin
of acid chloride groups in the polymer on the hexane flux and the
retention ndocosane.
TABLE C
__________________________________________________________________________
n-hexane toluene methanol
retention retention retention
Organic
n-docosane
flux n-docosane
flux PEG 300
flux
Vb phase (%) kg/(m.sup.2 .multidot. hour)
(%) kg/(m.sub.2 .multidot. hour)
(%) kg/(m.sup.2 .multidot. hour)
__________________________________________________________________________
IVa
freon 0 nil 0
IVb
toluene
36 137 54 197 high
IVc
toluene/
46 106 47 192 high
chloroform
(96/4 g/g)
IVd
toluene/ 0 77 87 82 71
n-hexane
(10/90 g/g)
__________________________________________________________________________
This example clearly demonstrates the large influence of the used organic
phase on the organic solvent flux and the retention behaviour.
TABLE D
__________________________________________________________________________
n-hexane toluene methanol
retention retention retention
n-docosane
flux n-docosane
flux PEG 300
flux
Example
Amine
% kg/(m.sup.2 .multidot. hour)
% kg/m.sup.2 .multidot. hour)
% kg/(m.sup.2 .multidot. hour)
__________________________________________________________________________
Va 2N 66 181 27 216 81 148
Vb 4N 73 99 24 291 74 100
Vc 6N 78 82 21 262 58 169
__________________________________________________________________________
TABLE E
______________________________________
n-hexane
triethyl amine
retention flux
Example perc., by weight,
n-docosane (kg/m.sup.2 .multidot. hour)
______________________________________
VI 1,0 77 65
VIa -- 56 147
______________________________________
TABLE F
__________________________________________________________________________
toluene/n-hexane
copolymer i-BMA/TFEA/AC
n-hexane toluene
Organic phase perc.,
retention retention
solvent ratio
molar
intr.*
by n-docosane
flux n-docosane
flux
Vb (g/g) ratio
(dl/g)
weight,
(%) kg/(m.sup.2 .multidot. h.)
(%) kg/(m.sup.2 .multidot.
__________________________________________________________________________
h.)
VIIa
16/84 95/--/5
0.53 0.53 74 35 54 152
VIIb
20/80 70/25/5
0.52 0.62 85 10 77 108
VIIc
43/47 47/48/5
0.57 0.59 0 85 57
__________________________________________________________________________
*Evaluated in acetone, c = 0,5
TABLE G
__________________________________________________________________________
toluene/n-hexane
copolymer i-BMA/TFEA/AC
n-hexane toluene
Organic phase perc.,
retention retention
solvent ratio
molar
intr.*
by n-docosane
flux n-docosane
flux
Vb (g/g) ratio
(dl/g)
weight,
(%) kg/(m.sup.2 .multidot. h.)
(%) kg/(m.sup.2 .multidot.
__________________________________________________________________________
h.)
VIIa
16/84 95/--/5
0.53 0.53 74 35 54 152
VIIIa
23/76 72/23/5
0.47 0.59 nil 81 59
VIIIb
70/30 --/95/5
0.84 0.59 0 60 138
__________________________________________________________________________
*Evaluated in acetone, c = 0,5
TABLE H
__________________________________________________________________________
toluene methanol
Copolymer i-BMA/AZ/AC
retention retention
Molar perc.,
n-docosane
flux n-docosane
flux
Vb ratio
intr.*
by weight,
(%) kg/(m.sup.2 .multidot. h.)
(%) kg/(m.sup.2 .multidot. h.)
__________________________________________________________________________
XIa
95/--/5
0,53
1,84 nil
XIb
95/--/5
1,96
1,89 nil 0
XIc
93/2/5 1,79 77 42 64 27
__________________________________________________________________________
*Evaluated in acetone, c = 0,5
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